Citation: CHEN Xing-yue, SHI Yi-ming, LIU Dan, DAI Cheng-yi, MA Xiao-xun. Catalytic performance of surface silicon-rich ZSM-5 zeolites in the co-production of lower olefins and p-xylene from methanol[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(4): 495-504. shu

Catalytic performance of surface silicon-rich ZSM-5 zeolites in the co-production of lower olefins and p-xylene from methanol

School of Chemical Engineer, Northwest University, International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon, Resources Chemical Engineering Research Center of the Ministry of Education for Advance Use, Technology of Shanbei Energy, Shanxi Research Center of Engineering Technology for Clean Coal Coversion, Collaborative Innovation, Center for Shanbei Energy and Chemical Industry, Xi'an 710069, China

Corresponding author: MA Xiao-xun, maxym@nwu.edu.cn
Received Date: 22 January 2020
Revised Date: 18 March 2020

Figures(6)

Surface silicon-rich ZSM-5 zeolites were prepared by surface chemical modification; their pore structure and acid properties were characterized by XRD, nitrogen sorption, TEM, NH₃-TPD and Py-FTIR spectroscopy. The catalytic performance of modified ZSM-5 zeolites in the conversion of methanol to p-xylene and lower olefins was investigated. The results show that the introduction of Zn in ZSM-5 can change part of the strong acid sites into the medium ones and increase the Zn-Lewis acid sites with dehydrogenation capacity, which can enhance the selectivity to ethene and propene. The modification with Mg can not only adjust the pore shape selectivity, but also increase the amount of Lewis acid sites, which is beneficial to the formation of p-xylene. Through multiple silicon depositions from different silicon sources, SiO₂ is uniformly deposited on the outer surface of modified ZSM-5 catalysts, which can modulate the acid properties and pore structure and thereby further improve the selectivity to p-xylene and ethene and propene. By using these modification approaches, the selectivity to p-xylene and ethene and propene reaches 61%, with 87.1% of p-xylene in the xylenes product, 97.8% of ethene in C₂ hydrocarbons, and 90.6% of propene in C₃ hydrocarbons.
- p-xylene,
- shape-selective catalysis,
- silicon deposition,
- light olefins,
- ZSM-5
1. [1]
  WU Chuan, WANG Jing-yi, LU Jun-yue, WANG Xiao-dong, LIU Bao-he, HUANG Pei, SHI Jun. Research progress on separation for para-xylene[J]. J Nanjing Univ Technol, 2002,24(3):106-110.
2. [2]
  FENG Zhi-qiang. PX crystallization separation technology and reconstruction of aromatic plant[J]. Mod Chem Ind, 2015,35(4):142-145.
3. [3]
  HAO Xi-wei, LIU Qiu-fang, LIU Gong, ZHANG Ya-qin, ZHANG Shi-gang. Progress and prospect of p-xylene production technologies[J]. Clean Coal Technol, 2016,22(5):25-30.
4. [4]
  WU Wei. Advances and development of aromatics production technologies for an aromatics complex[J]. Acta Pet Sin(Pet Process Sect), 2013,31(2):275-281.
5. [5]
  KONG De-jin, YANG Wei-min. Advance in technology for production of aromatic hydrocarbons[J]. Chem Ind Eng Prog, 2011,30(1):16-25.
6. [6]
  CHEN Liang, XIAO Jian, XIE Zai-ku, YU Jian-guo. Advances in p-xylene separation by crystalization[J]. Mod Chem Ind, 2009,29(2):10-14.
7. [7]
  FAN Jing-xin, YU Hai-bin, ZANG Jia-zhong, XING Shu-jian. Research progress in selective alkylation of toluene and methanol[J]. Ind Catal, 2013,21(6):1-4.
8. [8]
  LI Zhao-qing. Study on catalyst for alkylation of toluene with methanol for preparing p-xylene and low-carbon olefin[D]. Beijing: China University of Petroleum, 2016.
9. [9]
  LI J H, TONG K, XI Z W, YUAN Y, HU Z H, ZHU Z R. Highly-efficient conversion of methanol to p-xylene over shape-selective Mg-Zn-Si-HZSM-5 catalyst with fine modification of pore-opening and acidic properties[J]. Catal Sci Technol, 2016,6:4802-4813.
10. [10]
  GUAN Wen-bin, XIN Yu-bin, WEI Li-hu, ZHANG Shi-gang. Research progress on para-xylene synthesis by aromatization of methanol[J]. Coal Chem Ind, 2019,47(2):11-15.
11. [11]
  ZHANG G Q, ZHANG X, BAI T, CHEN T F, FAN W T. Coking kinetics and influence of reaction-regeneration on acidity, activity and deactivation of Zn/HZSM-5 catalyst during methanol aromatization[J]. J Energy Chem, 2015,24(1):108-118.
12. [12]
  ZHANG Zhi-zhi, QIN Zhang-feng, WANG Guo-fu, WANG Jian-guo. Toluene disproportion over HZSM-5 under near critical coditions[J]. J Fuel Chem Technol, 2005,33(1):96-100.
13. [13]
  ONO Y. Transformation of lower alkanes into aromatic hydrocarbons over ZSM-5 zeolites[J]. Catal Rev:Sci Eng, 1992,34(3):179-226.
14. [14]
  ZAIDI H A, PANT K K. Catalytic conversion of methanol togasoline range hydrocarbons[J]. Catal Today, 2004,96(3):155-160.
15. [15]
  ZHANG J G, QIAN W Z, KONG C Y, WEI F. Increasing para-xylene selectivity in making aromatics from methanol with a surface-modified Zn/P/ZSM-5 catalyst[J]. ACS Catal, 2015,5(5):2982-2988.
16. [16]
  NI Y M, SUN A M, Wu X L, HAI G L, HU J L, LI T, LI G X. The preparation of nano-sized H[Zn, Al]ZSM-5 zeolite and its application in the aromatization of methanol[J]. Microporous Mesoporous Mater, 2011,143(2/3):435-442.
17. [17]
  ZHANG Zhi-ping, ZHAO Yan, WU Hong-yu, TAN Wei, WANG Xiang-sheng, GUO Xin-wen. Shape-selective alkylation of toluene with methanol over modified nano-scale HZSM-5 zeolite[J]. Chin J Catal, 2011,32(7):1280-1286.
18. [18]
  HU Q F, HUANG X F, CUI Y, LUO T F, TANG X P, WANG T, QIAN W Z, WEI F. High yield production of C_{2, 3} olefins and para-xylene from methanol using a SiO₂-coated FeO_x/ZSM-5 catalyst[J]. RSC Adv, 2017,7(46):28940-28944.
19. [19]
  MIYAKE K, HIROTA Y, ONO K, UCHIDA Y, TANAKA S, NISHIYAMA N. Direct and selective conversion of methanol to para-xylene over Zn ion doped ZSM-5/silicalite-1 core-shell zeolite catalyst[J]. J Catal, 2016,342:63-66.
20. [20]
  PAN D H, SONG X H, YANG X H, GAO L J, WEI R P, ZHANG J, XIAO G M. Efficient and selective conversion of methanol to para-xylene over stable H[Zn, Al]ZSM-5/SiO₂ composite catalyst[J]. Appl Catal A:Gen, 2018,557:15-24.
21. [21]
  LIANG T Y, CHEN J L, QIN Z F, LI J F, WANG P F, WANG S, WANG G F, DONG M, FAN W B, WANG J G. Conversion of methanol to olefins over HZSM5 zeolite:Reaction pathway is related to the framework aluminum siting[J]. ACS Catal, 2016,6(11):7311-7325.
22. [22]
  ZHONG Bing, LUO Qing-yun, XIAO You-xie, ZHANG Wei. Reaction mechanism of methanol to hydrocarbons on HZSM-5[J]. J Fuel Chem Technol, 1986,14(1):9-16.
23. [23]
  WANG Jin-ye, WANG Ding-zhu, LU Xue-dong, DOU Xiu-yun. Conversion of lower alcohols into aromatics over cation-modified HZSM-5 zeolites[J]. Chin J Catal, 1993,14(3):324-327.
24. [24]
  CAO Jin-song, ZHANG Jun-min, XU Lei, LIU Zhong-min. Superiorities for developing PX production process through alkylation of toluene alcohol[J]. Technol Econ Petrochem, 2010,26(1):8-10.
25. [25]
  ZHONG J W, HAN J F, WEI Y X, XU S T, SUN T T, GUO X W, SONG C S, LIU Z M. The template-assisted zinc ion incorporation in SAPO-34 and the enhanced ethylene selectivity in MTO reaction[J]. J Energy Chem, 2019,32:174-181.
26. [26]
  ZHONG J W, HAN J F, WEI Y X, XU S T, SUN T T, GUO X W, SONG C S, LIU Z M. Enhancing ethylene selectivity in MTO reaction by incorporating metal species in the cavity of SAPO-34 catalysts[J]. Chin J Catal, 2019,39(11):1821-1831.
27. [27]
  REN S, LIU G, WU X. Enhanced MTO performance over acid treated hierarchical SAPO-34[J]. Chin J Catal, 2017,38:123-130.
28. [28]
  LI L B, LIN R B, KRISHNA R, LI H, XIANG S C, WU H, LI J P, ZHOU W, CHEN B L. Ethane/ethylne separation in a metal-organic framework with iron-peroxo sites[J]. Sci, 2018,362(6413):443-446.
29. [29]
  JIA Y M, WANG J W, ZHANG K, WEI F, LIU S B, DING C M, LIU P. Promoted effect of zinc-nickel bimetallic oxides supported on HZSM-5 catalysts in aromatization of methanol[J]. J Energy Chem, 2017,26(3):540-548.
30. [30]
  WANG Yu, ZHAO Bi-ying, XIE You-chang. Correlations between the dispersion state of MgO and catalytic behavior of MgO/HZSM-5[J]. Acta Phys-Chim Sin, 2001,17(11):966-971.
31. [31]
  HAN Li-hua, LIU Ping, GAO Jun-hua, ZHOU Hao, SUN Xiao-fang, LIU Zeng-hou, ZHANG Kan. Si, P and Mg-modified HZSM-5 catalyst for enhancing the para-selectivity in toluene/methanol alkylation[J]. Nat Gas Ind, 2019,44(3):1-6.
32. [32]
  JANG H G, MIN H K, HONG S B, SEO J. Tetramethylbenzenium radical cations as major active intermediates of methanol-to-olefin conversions over phosphorous-modified HZSM-5 zeolites[J]. J Catal, 2013,299:240-248.
33. [33]
  WANG Sen, CHEN Yan-yan, WEI Zhi-hong, QIN Zhang-feng, LI Jun-fen, DONG Mei, FAN Wei-bin, WANG Jian-guo. Recent research progresses in the effect of framework structure and acidity of zeolites on their catalytic performance in methanol to olefins (MTO)[J]. J Fuel Chem Technol, 2015,43(10):1201-1214.
34. [34]
  BARTHOS R, LONYI F, ONYESTYAK G, VALYON J. An IR, FR, and TPD Study on the acidity of H-ZSM-5, sulfated zirconia, and sulfated zirconia-titania using ammonia as the probe molecule[J]. J Phys Chem B, 2000,104(31):7311-7319.
35. [35]
  KATADA N, IGI H, KIM J H, NIWA M. Determination of the acidic properties of zeolite by theoretical analysis of temperature-programmed desorption of ammonia based on adsorption equilibrium[J]. J Phys Chem B, 1997,101(31):5969-5977.
36. [36]
  TAN W, LIU M, ZHAO Y, HOU K K, WU H Y, ZHANG A F, LIU H O, WANG Y R, SONG C S, GUO X W. Para-selective methylation of toluene with methanol over nano-sized ZSM-5 catalysts:Synergistic effects of surface modifications with SiO₂, P₂O₅ and MgO[J]. Microporous Mesoporous Mater, 2014,196(15):18-30.
37. [37]
  WOOLERY G L, KUEHL G H, TIMKEN H C, CHESWER A W, VARTULI J C. On the nature of framework Brønsted and Lewis acid sites in ZSM-5[J]. Zeolites, 1997,19(4):288-296.
38. [38]
  TOPSOE N Y, PEDERSEN K, DEROUANE E G. Infrared and temperature-programmed desorption study of the acidic properties of ZSM-5-type zeolites[J]. J Catal, 1981,70(1):41-52.
39. [39]
  TONG Kai, LI Jun-hui, XI Zhi-wen, ZHU Zhi-rong. Study of methanol shape-selective aromatization over ZnO/SiO₂/ZSM-5 modified with mental oxide and silicon deposition[J]. J Fuel Chem Technol, 2015,43(2):221-227.
40. [40]
  LIU Wei-qiao, LEI Wei-ning, SHANG Tong-ming. Physicochemical and methanol aromatization property of HZSM-5 catalyst promoted by Zn[J]. Chem Ind Eng Prog, 2011,30(9):1967-1971.
41. [41]
  ZHAO Huan-yu, LIU Yun-qi, LIU Ping, ZHANG Xiu-bin, LIU Chen-guang. Effects of ZSM-5 zeolite catalysts modification conditions by liquid Si deposition on toluene disproportionation reaction[J]. J China University of Petroleum(Nat Sci Edi), 2006,30(6):117-120.
42. [42]
  ZHU X L, ZHANG J Y, CHENG M, WANG G W, YU M X, LI C Y. Methanol aromatization over Mg-P-modified[Zn, Al]ZSM-5 zeolites for efficient coproduction of para-xylene and light olefins[J]. Ind Eng Chem Res, 2019,58(42):19446-19455.
43. [43]
  ZHANG Xiu-bin, LI Qi-feng, LIU Yu-qi, LIU Chen-guang. Toluene disproportionation over ZSM-5 zeolite modified by phosphorus and magnesium[J]. Ind Catal, 2004,12(2):40-45.
44. [44]
  LI Y, JUN H. Kinetics study of the isomerization of xylene on ZSM-5 zeolites:the effect of the modification with MgO and CaO[J]. Appl Catal A:Gen, 1996,142(1):123-137.
45. [45]
  NIU X J, GAO J, MIAO Q, DONG M, WANG G F, FAN W B, QIN Z F, WANG J G. Influence of preparation method on the performance of Zn-containing HZSM-5 catalysts in methanol-to-aromatics[J]. Microporous Mesoporous Mater, 2014,197:252-261.
46. [46]
  CHANG C D, LANG W H, SMITH R L. The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts[J]. J Catal, 1979,56(2):169-173.
47. [47]
  LI Ling-ling, NIE Xiao-wa, SONG Chun-shan, GUO Xin-wen. Isomerization mechanism of xylene catalyzed by H-ZSM-5 molecular sieve[J]. Acta Phys-Chim Sin, 2013,29(4):754-762.
48. [48]
  VALECILLOS J, EPELDE E, ALBO J, AGUAYO A T, BILBAO J, CASTANO P. Slowing down the deactivation of H-ZSM-5 zeolite catalyst in the methanol-to-olefin (MTO) reaction by P or Zn modifications[J]. Catal Today, 2019.
49. [49]
  KAEDING W W, CHU C, YOUNG L B, WEINSTEIN B, BUTTER S A. Selective alkylation of toluene with methanol to produce para-xylene[J]. J Catal, 1981,67(1):159-174.
50. [50]
  YASHIMA T, SAKAGUCHI Y, NAMBA S. Selective formation of p-xylene by alkylation of toluene with methanol on ZSM-5 type zeolites[J]. Stud Surf Sci Catal, 1981,7(Part A):739-751.
51. [51]
  ZHU Jie, CUI Yu, CHEN Yuan-jun, ZHOU Hua-qun, WANG Yao, WEI Fei. Recent researches on process from methanol to olefins[J]. J Chem Ind Eng, 2010,61(7):1674-1684.
52. [52]
  PAN Hong-yan, TIAN Min, HE Zhi-jie, HUA Kai-hui, LIN Qian. Advances in research on modified ZSM-5 molecular sieves for conversion of methanol to olefins[J]. Chem Ind Eng Prog, 2014,33(10):2625-2633.
53. [53]
  TENG H, WANG J, REN X Q, CHEN D M. Disproportionation of toluene by modified ZSM-5 zeolite catalysts with high shape-selectivity prepared using chemical liquid deposition with tetraethyl orthosilicate[J]. Chin J Chem Eng, 2011,19(2):292-298.
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Catalytic performance of surface silicon-rich ZSM-5 zeolites in the co-production of lower olefins and p-xylene from methanol

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com